Radiation-sensitive mixture

ABSTRACT

A radiation-sensitive mixture which contains (a) a compound of the formula (I) ##STR1## where R 1  is an optionally substituted alkyl radical, R 2  is a hydrogen atom or an optionally substituted alkyl radical containing 1 to 4 carbon atoms, R 3  is an n-valent, optionally polymeric aliphatic or aromatic radical and n is a number from 1 to 100; and b) a compound which forms a strong acid on exposure to actinic radiation.

This application is a division of application Ser. No. 08/567,775, filedDec. 5, 1995 now U.S. Pat. No. 5,705,317.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a radiation-sensitive, in particularphotosensitive, mixture which contains

(a) a compound having at least one acid-cleavable C--O--C bond, and

(b) a compound which forms a strong acid on exposure to actinicradiation.

The invention also relates to methods of forming images using suchmixtures and to acid-cleavable compounds useful in such mixtures.

2. Description of Related Art

Positive-working photosensitive mixtures whose exposed areas are moresoluble in an aqueous alkaline developer liquid than the unexposedregions are known. In particular, positive-working recording materialsbased on o-quinone diazides have gained acceptance in practice.

The photosensitivity of these materials is frequently unsatisfactory. Anincrease in the photosensitivity can be achieved by using catalyticallyactive photosensitive systems since the quantum yield becomes greaterthan 1 in such systems. Thus, the known principle of initiatingsecondary reactions by means of photolytically produced acids andthereby inducing an increased solubility of the exposed regions has beenused recently for positive-working systems. Under these circumstances,photochemically produced strong acids serve to cleave acid-labilecompounds whose cleavage products have a greater solubility in aqueousalkaline developers than the original compounds.

Low-molecular-weight and high-molecular-weight acetals and O,N-acetalscontaining aromatic compounds as hydroxyl or amino component (see U.S.Pat. No. 3,779,778), and also ortho esters and amide acetals (see DE-C26 10 842) are used as acid-cleavable compounds. Radiation-sensitivepositive-working mixtures are also obtained using polymeric ortho esters(See EP-B 0 022 571) and polymeric aliphatic acetals (See DE-C 27 18254). Such mixtures are frequently unsatisfactory since the cleavageproducts obtained by acid-catalyzed fragmentation are often onlyinadequately soluble in aqueous alkalis and therefore result in problemsin the development of such layers. In addition, many of the compoundsmentioned can only be obtained with difficulty. In other cases, thestorage life of the recording materials concerned is unsatisfactory inthe unexposed state.

Polymers containing acid-labile tert-butyl carbonate groupings ortert-butyl carboxylate groupings which function positively in mixtureswith photochemical acid donors are described in EP-B 0 102 450 and EP-A0 366 590. An extrapolation of this principle to molecules having amolecular weight below 500 in combination with conventional binders isto be found in EP-B 0 249 139. Such systems are also not free ofdisadvantages: the reduced solubility inhibition of the binder matrixcompared with o-quinone diazides is manifested in an unduly lowresistance of the unexposed regions in the developer (so-called darkerosion) and consequently in a poor differentiation between exposed andunexposed regions.

SUMMARY OF THE INVENTION

An object of the invention was to provide radiation-sensitive mixtureswhich have high sensitivity to actinic radiation, in particularshort-wave light, and which make possible a good differentiation betweenexposed and unexposed regions and which have a high storage life in theunexposed state. Within the scope of this description, actinic radiationis to be understood as meaning any radiation whose energy corresponds atleast to that of visible light. Long-wave UV radiation, in particular,is suitable, but so are electron radiation, X-rays and laser radiation.

It is also an object of the invention to provide compounds that haveacid-cleavable C--O--C bonds useful in radiation-sensitive mixtures, andto provide methods of forming images with such mixtures.

In accordance with these objectives, there has been provided aradiation-sensitive mixture which include

(a) a compound having at least one acid-cleavable C--O--C bond and

(b) a compound which forms a strong acid on exposure to actinicradiation.

In particular the mixture according to the invention is one wherein thecompound (a) is a compound of the formula I ##STR2## where R¹ is anoptionally substituted alkyl radical,

R² is a hydrogen atom or an optionally substituted alkyl radicalcontaining 1 to 4 carbon atoms,

R³ is an n-valent, optionally polymeric aliphatic or aromatic radicaland

n is a number from 1 to 100.

The R¹ and R² groups may be the same or different in the n repeatingunits.

In accordance with these objectives, there is also provided a processfor forming an image comprising

(a) exposing the radiation-sensitive mixture described above, and

(b) developing the exposed material.

Further objects, features, and advantages of the invention will becomeapparent from the detailed description of preferred embodiments thatfollows.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Any compound or mixture of compounds having the formula (I) may be usedin the present invention. In the compounds of the formula (I), theradical R¹ may be a saturated or unsaturated, linear or branched,substituted or unsubstituted alkyl radical. Any substituents which donot adversely affect the compound of formula (I) may be used. Suitablesubstituents include, for example, halogen atoms, in particular fluorineatoms, alkoxy groups containing 1 to 4 carbon atoms, and phenylradicals. More than one substituent can be present. The total number ofcarbon atoms in R¹ should generally not be greater than 10. Particularlypreferred for R¹ are unsubstituted, linear or branched alkyl radicalscontaining 1 to 6, in particular 1 to 4, carbon atoms. Secondary andtertiary alkyl radicals are particularly advantageous.

R² is hydrogen or an alkyl radical, for example, as described for R¹,preferably containing 1 to 4 carbon atoms. The radical R² is preferablya hydrogen atom, or a methyl or ethyl group.

In formula (I), n is an integer from 1 to 100.

In the low-molecular-weight acylals within the scope of formula (I), nis a number from 1 to 4, preferably 2 or 3. For high molecular weightacylals, n is preferably at least about 10.

R³ may be any low-molecular-weight or high-molecular-weight group. As alow-molecular-weight group, R³ may be aliphatic, cycloaliphatic, oraromatic. Preferred are groups which contain at least one, preferably 1to 3, aromatic nuclei, i.e., benzene rings. These may be joined to oneanother by fusion or by linking by means of an intermediate member. Theintermediate member may be, inter alia, a single bond or one of thegroups --O--, --S--, --SO--, --SO₂ --, --SO₂ --O--, --CO-- or--C(R⁴)(R⁵)--, where R⁴ and R⁵ are identical or different and arehydrogen atoms, methyl groups, or trifluoromethyl groups. The aromaticnuclei may be substituted, for example, by halogen atoms, alkyl oralkoxy groups containing 1 to 3 carbon atoms, alkanoyl or alkoxycarbonylgroups containing 2 to 5 carbon atoms or carboxyl groups.

If R³ is an aliphatic group, it generally has 1 to 10, preferably 1 to6, carbon atoms and may be interrupted by ethereal oxygen atoms orphenylene groups and contain double bonds. Suitable as cycloaliphaticgroups R³ are preferably those containing 5 or 6 ring members. They maycontain one or two rings which are optionally linked by identicalintermediate members such as the aromatic rings.

If R³ is a polymeric group, it may contain up to approximately 100 unitshaving lateral carboxyl groups and be derived from a homopolymer orcopolymer. Suitable as comonomer units are nonacidic vinyl monomerunits, for example, composed of olefins, vinyl ethers, vinyl esters,(meth)acrylates, maleates or vinylaromatics. The carboxylic acid unitsmay be derived from α,β-unsaturated carboxylic acids, such as(meth)acrylic acid, maleic acid or maleic anhydride, crotonic acid,vinylbenzoic acid and the like. The molecular weight M_(w) of thepolymer containing carboxyl groups may be in the range from 5,000 to200,000, preferably from 20,000 to 100,000. Copolymers of (meth) acrylicacid with (meth)acrylates are particularly preferred.

The acid-cleavable acylals of formula (I) are prepared in any desiredmanner, and are preferably prepared from the basic carboxylic acids R³(COOH)_(n) by reaction with carboxylic esters of the formula R¹--CO--O--CHR² --X, where X is a halogen atom, in particular Cl or Br.The reaction takes place in the presence of organic bases, for example,of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The esters containing R¹=tert-butyl are particularly well suited since, in the case of thelatter, the tendency to side reactions is largely suppressed by thesteric screening of the carbonyl group. The polymeric acylals may alsobe prepared by polymerization of monomers containing acylal groups. Inprinciple, polymers containing acylal groups in the main chain may alsobe used as acid-cleavable compounds in the mixtures according to theinvention.

Examples of suitable R¹ --CO--O--CHR² X carboxylates includechloromethyl pivalate and 1-bromoethyl pivalate. Suitable as R³(COOH)_(n) carboxylic acids are: aliphatic mono- or polycarboxylic acidssuch as hexanoic acid, malonic acid, propanetricarboxylic acid or1,2,3,4-butanetetracarboxylic acid and cycloaliphatic carboxylic acidssuch as 1,4-cyclohexanedicarboxylic acid. Particularly preferred arearomatic mono- and polycarboxylic acids such as benzoic acid, phthalicacid, isophthalic acid, terephthalic acid, benzene-1,3,5-tricarboxylicacid, 1,2,4,5-benzenetetracarboxylic acid, naphthalene-1-carboxylicacid, naphthalene-2-carboxylic acid, naphthalene-1,4-dicarboxylic acid,naphthalene-2,6-dicarboxylic acid, naphthalene-1,8-dicarboxylic acid,naphthalenetricarboxylic acids, naphthalene-1,4,5,8-tetracarboxylicacid, biphenyl-4-carboxylic acid, biphenyl-4,4'-dicarboxylic acid,diphenyl ether 4,4'-dicarboxylic acid, benzophenone-2-, -3-, and-4-carboxylic acid, 4-carboxyphenyl 4-carboxybenzenesulfonate,bis(4-carboxyphenyl)sulfone, bis(4-carboxyphenyl)methane and2,2-bis(4-carboxyphenyl)propane. Generally, any mono- or polycarboxylicacid is suitable which, on the one hand, is nucleophilic enough underthe chosen reaction conditions to enter into the desired reaction toform the acylal and, on the other hand, apart from carboxyl groups,contains no further groups capable of reacting with R¹ CO--O--CHR² Xcarboxylates under the chosen reaction conditions.

To produce the positive-working, radiation-sensitive mixtures accordingto the invention, the high-molecular-weight or low-molecular-weightacylals described of the formula

    [R.sup.1 CO--O--CHR.sup.2 13 O--CO--].sub.n R.sup.3

are mixed with substances which form acid photochemically or as a resultof exposure to high-energy rays, and optionally with binders. Thequantitative proportion of the acylals in the total solids of themixtures are an effective amount to give the desired effect andgenerally are between 10 and 95, preferably 30 to 90% by weight; ifbinders are used, between 5 and 50, preferably between 10 and 30% byweight. As a result of using different acylals or mixtures of the same,the material properties of the recording materials produced therewithcan be varied widely. Since aqueous alkaline solutions canadvantageously be used as developer liquid for the exposed printinglayers and such solutions are generally preferred to developers based onorganic solvents, those binders are preferred, in particular, which aresoluble or at least swellable in aqueous alkalis.

Any desired binders can optionally be used in the mixture of the presentinvention. Particularly suitable as binders are the phenolic resins usedin many positive printing materials, in particular cresol-formaldehydenovolaks (generally having a melting range 105-120° C. according to DIN53 181) and phenol-formaldehyde novolaks (generally having a meltingrange 110-120° C. according to DIN 53 181). Polymers containing phenolicOH groups, for example, polyhydroxystyrene and its copolymers withneutral aliphatic or aromatic monomers are also suitable.

The nature and amount of water-insoluble binder may be differentdepending on the application purpose; generally, its proportion of thetotal solids is between 0 and 95, preferably 20 to 90% by weight. If theacid-cleavable acylal is not itself polymeric, 50 to 95, preferably 70to 90% by weight of binder are generally used.

Also suitable for use in the mixture according to the invention arebinders whose alkali solubility is increased by exposure to acid. Suchbinders may be prepared, for example, by providing the phenolic OHgroups of commercial polyhydroxystyrene binders with acid-labile groupswhich reduce the alkali solubility.

Other alkali-soluble resins such as copolymers of methacrylic acid andmethyl methacrylate, vinyl acetate and crotonic acid, maleic anhydrideand styrene and the like are also suitable as binders.

To prepare the radiation-sensitive mixtures according to the invention,the acid-cleavable compounds containing acylal groups are mixed with thebinder (if binder is used) and also with one or more substances whichform a strong acid photochemically or by exposure to high-energy rays.The addition of a binder is not necessary if the acylal itself ispolymeric. In this case, the polymeric acylal may contain free carboxylgroups; this is not, however, necessary since, in the case oflight-induced cleavage of the acylal groups, sufficient free carboxylgroups are formed to make the exposure product alkali-soluble.

In addition, numerous other polymers can also be used in theradiation-sensitive mixtures according to the invention. Preferablyvinyl polymers such as polyvinyl acetates, poly(meth)acrylates,polyvinyl ethers, and polyvinylpyrrolidones, which may themselves bemodified by comonomers. The most favorable proportion of these polymersdepends on the application requirements and the effect on thedevelopment conditions and is generally not more than 20% of the totalsolids content. In small amounts, the photosensitive layer may alsocontain, in addition, substances such as polyglycols, cellulosederivatives such as ethylcellulose, wetting agents, dyes and finelydivided pigments for special requirements such as flexibility, adhesion,gloss, and the like.

Any desired compound or compounds that forms or releases an acid thatwill cleave the acid-cleavable compound of formula (I) can be used ascompound (b) of the inventive mixture. For example, a large number ofknown compounds and mixtures, such as onium salts, for example,diazonium, phosphonium, sulfonium and iodonium salts, halogen compounds,(o-quinone diazide)sulfonyl chlorides, (o-quinone diazide)sulfonates and(o-quinone diazide)sulfonamides and also organometal/organohalogencombinations are suitable for use in the radiation-sensitive mixturesaccording to the invention as radiation-sensitive components which, onirradiation, preferably form or eliminate strong acids.

The onium compounds mentioned are generally used in the form of theirsalts which are soluble in organic solvents, for example, thesulfonates, trifluoromethanesulfonates and hexafluoropropanesulfonates,or as precipitation products with complex acids such as tetrafluoroboricacid, hexafluorophosphoric acid, hexafluoroantimonic andhexafluoroarsenic acid. The diazonium salts are particularly preferred.

Halides, esters, and amides of the positive-working o-quinone diazidescan also be used. Of this group, (naphthoquinone1,2-diazide(2))-4-sulfonyl chloride is preferred.

Basically, all the organic halogen compounds also known as photochemicalfree-radical starters can be used as halogen-containingradiation-sensitive compounds which form hydrohalic acid, for example,those containing more than one halogen atom on a carbon atom or on anaromatic ring. Examples are described in U.S. Pat. No. 3,779,778, DE-C26 10 842 and DE-A 27 18 259 and DE-A 22 43 621. These documents areincorporated by reference in their entireties. The sensitivity of thesehalogen-containing compounds can be influenced spectrally and increasedby the known sensitizers.

Examples of particularly suitable acid donors for use in theradiation-sensitive mixture according to the invention as compound (b)include: (naphthoquinone 1,2-diazide(2))-4-sulfonylchloride;4-(di-n-propylamino)benzenediazonium tetrafluoroborate,hexafluorophosphate and trifluoromethanesulfonate;2,5-diethoxy-4-(4-tolylmercapto)benzenediazonium tetrafluoroborate,hexafluorophosphate, trifluoromethanesulfonate andhexafluoropropanesulfonate; diphenylamine-4-diazonium sulfate and4-diethylaminobenzenediazonium trifluoromethanesulfonate, and also thecompounds cited in the examples which follow.4-Methyl-6-trichloromethyl-2-pyrone,4-(3,4,5-trimethoxystyryl)-6-trichloromethyl-2-pyrone,2-trichloromethylbenzimidazole, 2-tribromomethylquinolone,2,4-dimethyl-1-tribromoacetylbenzene, 3-nitro-1-tribromoacetylbenzene,4,6-bis-trichloromethyl-s-triazines such as 2-(6-methoxy-2-naphthyl)-,2-(1-naphthyl)-, 2-(4-ethoxyethyl-1-naphthyl)-, 2-(3-benzopyranyl)-,2-(9-phenanthryl)- and2-(4-methoxy-1-anthracyl)-4,6-bis-trichloromethyl-s-triazine can also beused.

The amount of starter compound (b) may be varied depending on itschemical nature and the composition of the mixture. In general,approximately 0.1 to 40% by weight, based on the total solids,preferably 0.2 to 25% by weight, are used. For layers having thicknessesof over 10 μm, in particular, it is advisable to use relatively littleacid donor.

Soluble or, alternatively, finely dispersed dispersible dyes and also,depending on the application purpose, UV absorbers, may additionally beadded to the photosensitive mixtures. The triphenylmethane dyes, inparticular in the form of their carbinol bases, have proved particularlyadvantageous as dyes. The most favorable quantitative ratio of thecomponents can easily be determined in the individual case bypreliminary experiments.

Suitable solvents for the radiation-sensitive mixture according to theinvention include ketones such as methyl ethyl ketone, chlorinatedhydrocarbons such as trichloroethylene and 1,1,1-trichloroethane,alcohols such as n-propanol, ethers such as tetrahydrofuran, alcoholethers such as propylene or ethylene glycol monomethyl ether, and esterssuch as butyl acetate. It is also possible to use mixtures which mayalso contain, in addition, solvents such as acetonitrile, dioxane ordimethylformamide for specific purposes. In principle, and solvents canbe used which do not react irreversibly with the layer components.

Compared with other positive layers, particularly those based ono-naphthoquinone diazide, the production of thicker layers, i.e. layersthicker than about 10 μm, is advantageously possible with the presentinvention since the dependence of the photosensitivity of the mixturesaccording to the invention on thickness is relatively low. Exposure andprocessing of layer thicknesses up to approximately 100 μm and above ispossible.

The radiation-sensitive mixtures of the invention may be coated on anydesired substrate. Preferred bases of layers having thicknesses of morethan 10 μm are plastics films which then serve as temporary bases fortransfer layers. For the latter and for color films, polyester films,for example, composed of polyethylene terephthalate, are preferred.Polyolefin films, for example, polypropylene films, are also suitable.

Metals are generally used as layer bases for layer thicknesses belowapproximately 10 μm. The following may be used for offset printingplates: mechanically or electrochemically grained and optionallyanodized aluminum which, in addition, may also be chemically pretreated,for example, with polyvinylphosphonic acid, silicates or phosphates, andin addition multi-metal plates containing Cu/Cr or brass/Cr as uppermostlayer.

For letterpress plates, the mixtures according to the invention may beapplied to zinc or magnesium plates and also their commercialmicrocrystalline alloys for powderless etching, and also to etchableplastics such as polyoxymethylene. For gravure or screen-printing forms,the mixtures according to the invention are suitable on copper or nickelsurfaces as a result of good adhesion and resistance to etching. Theycan also be used as photoresists and in chemical milling.

The substrate is coated in any desired manner. For example, coating canbe carried out directly or by dry layer transfer from the temporary baseonto printed circuit board materials which are composed of insulatingboards having single-sided or double-sided copper cladding, onto glassor ceramic materials which have optionally been pretreated in anadhesion-promoting manner and, inter alia, onto silicon wafers on whosesurface there is optionally a nitride or oxide layer. In addition, it ispossible to coat wood, textiles, and surfaces of many materials whichare advantageously imprinted by projection and are resistant to exposureto alkaline developers.

The coated mixture on the substrate, may be dried as desired. Theconventional appliances and conditions can be adopted for the dryingafter coating; temperatures of around 100° C. and, for short periods, ofup to 120° C. are tolerated without loss of radiation sensitivity.

The coated substrate may be processed as desired. For the exposure, usemay be made of the conventional light sources such as tubular lamps,xenon pulsed lamps, metal-halide-doped mercury-vapor high-pressure lampsand carbon-arc lamps. In addition, exposure in conventional projectionand enlargement appliances under the light of metal-filament lamps isuseful, as is contact exposure with conventional incandescent lamps. Theexposure can also be carried out with the coherent light of a laser.Suitable for the purposes of the present invention are lasers of thecorrect power which emit in the UV or visible region, for example, argonion lasers, krypton ion lasers, dye lasers, helium-cadmium lasers andexcimer lasers. The laser beam is controlled by means of a specified,programmed line and/or raster movement.

Irradiation with electron beams is a further imprinting possibility. Asalso in the case of many other organic materials, electron beams areable to decompose and crosslink the mixture according to the inventionin a radical manner so that a negative image is formed if theunirradiated parts are removed by solvent or exposure without master anddevelopment. On the other hand, at fairly low intensity and/or fairlyhigh writing speed of the electron beam, the electron beam produces adifferentiation in the direction of higher solubility, i.e., theirradiated layer areas can be removed by the developer. The choice ofthe most favorable conditions can easily be determined by preliminaryexperiments.

The imagewise exposed or irradiated layer can be removed--optionallyafter a thermal aftertreatment--using virtually the same developers asfor commercial naphthoquinone diazide layers and photoresists, or thecopying conditions of the inventive material can be adaptedadvantageously to the known aids such as developers and programmed spraydevelopment appliances. Any desired developers can be used in anydesired developing process. The aqueous developer solutions may contain,for example, alkali metal phosphates, silicates or hydroxides and,furthermore, wetting agents, and also fairly small proportions oforganic solvents. In certain cases, pure water or solvent/water mixturesare also usable as developers. The most favorable developer can bedetermined by experiments with the layer used in a particular case. Ifnecessary, the development may be mechanically aided. To increase theresistance during printing and also the resistance to washing-outagents, deletion fluids and printing inks which can be cured by UVlight, the developed plates can be heated to elevated temperatures for ashort time, as is disclosed for diazo layers in GB-A 1 154 749.

Examples of preferred radiation-sensitive mixtures according to theinvention and a synthesis of the acid-cleavable acylals they contain arespecified below. The amounts are specified in parts by weight (pbw), andpercentages and quantitative ratios are to be understood in units ofweight. The examples are for illustrative purposes only and do not limitthe scope of invention.

EXAMPLES 1-12

Reaction of Carboxylic Acids With Pivalates to Form Acylals

1 equivalent of the carboxylic acid was dissolved or suspended inacetone. 1.1 equivalents of chloromethyl pivalate or 1-bromoethylpivalate were added per carboxylic acid unit. 1.1 equivalents of1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) per carboxylic acid unit werethen added dropwise at 0° C. Stirring was still continued for some timeat room temperature, or optionally at slightly elevated temperature,until the completion of the reaction (by thin-layer chromatography).After the DBU chloride or bromide precipitated had been filtered off bysuction, the solvent was distilled off in a rotary evaporator, theresidue was taken up in ethyl acetate and the solution was washed outconsecutively with 0.1 N HCl, NaHCO₃ solution and H₂ O. After dryingwith MgSO₄, concentration and optionally recrystallization were carriedout. The acylals listed in Table 1 were obtained.

                  TABLE 1                                                         ______________________________________                                        Synthesized acylals of the formula (I) with R.sup.1 = tert-butyl                No.      R.sup.2 R.sup.3        Mp[°C.]                                                                       n                                    ______________________________________                                        1      H       4,4'-oxydiphenyl 74-75  2                                        2 CH.sub.3  86-88 2                                                           3 H 1,3,5-benzenetriyl 75-77 3                                                4 CH.sub.3  103-104 3                                                         5 H 1,4-phenylene 88-89 2                                                     6 CH.sub.3  105-106 2                                                         7 H 4-benzoylphenyl 70-71 1                                                   8 CH.sub.3  63-64 1                                                           9 CH.sub.3 4,4'-sulfonyldiphenyl 88-91 2                                        (--C.sub.6 H.sub.4 --SO.sub.2 --C.sub.6 H.sub.4 --)                         10 CH.sub.3 4,4'-sulfonyloxydiphenyl 110-114 2                                  (--C.sub.6 H.sub.4 --SO.sub.2 O--C.sub.6 H.sub.4 --)                        11 H biphenyl-4,4'-diyl 118-119 2                                             12 CH.sub.3  150-153 2                                                      ______________________________________                                    

EXAMPLE 13

The compounds contained in Table 1 were processed to form solutions ofthe composition

5.00 pbw of novolak,

1.50 pbw of acylal in accordance with Table 1,

0.25 pbw of4-p-tolylmercapto-2,5-diethoxybenzenediazoniumhexafluorophosphate and

0.03 pbw of Crystal Violet base in

125.00 pbw of butanone,

applied by spinning to plates composed of electrochemically grained andanodized aluminum and dried at 100° C. in a drying oven, which processresulted in a layer thickness of 1.8 to 2.0 μm. The plates were exposedunder a 5 kW metal-halide lamp for 30 s at a distance of 110 cm througha continuous-tone stepped wedge having 13 steps with a density gradationof 0.15, heated for 2 minutes in a drying oven at 120° C. and developedin an aqueous alkaline developer of the composition

5.5 pbw of sodium metasilicate nonahydrate,

3.4 pbw of trisodium phosphate dodecahydrate,

0.4 pbw of anhydrous monosodium phosphate and

90.7 pbw of completely demineralized water.

Positive images of the film master were obtained.

EXAMPLE 14

This example shows the suitability of the radiation-sensitive mixturesaccording to the invention for use in offset printing plates.

A plate composed of electrochemically grained and anodized aluminum wascoated with a solution composed of

5.00 pbw of novolak,

1.50 pbw of acylal 10 according to Table 1,

0.25 pbw of 4-p-tolylmercapto-2,5-diethoxybenzenediazonium1,1,2,3,3,3-hexafluoropropanesulfonate and

0.03 pbw of Crystal Violet base in

125.00 pbw of butanone

and heated in a drying oven at 100° C., which process resulted in alayer thickness of 1.9 μm. The plate was exposed under a 5 kWmetal-halide lamp for 30 s at a distance of 110 cm through acontinuous-tone stepped wedge having 13 steps with a density gradationof 0.15, heated at 150° C. for 3 minutes and developed in the developerspecified in Example 13 for 30 s. A positive image of the film masterwas obtained; step 4 of the continuous-tone step wedge was completelyopen, while step 10 was reproduced in completely covered form. Whenclamped in an offset printing press, more than 60,000 good impressionswere obtained with this plate without detectable wear of the printinglayer.

EXAMPLE 15

5 pbw of a copolymer of methyl methacrylate and methacrylic acid (AN355, equivalent to 60 mol % methacrylic acid) were dissolved in 50 pbwof dimethylacetamide. 14.5 pbw of 1-bromoethyl pivalate were added and10.5 pbw of DBU were then added dropwise at 0° C. After 2 hours,precipitation was carried out at 50° C. in H₂ O and reprecipitation wascarried out yet again from acetone/H₂ O. 6.2 pbw of slightly yellowsolid in which no free acid groups could be detected were obtained.

EXAMPLE 16

A plate composed of electrochemically grained and anodized aluminum wasspin-coated with a solution composed of

9.00 pbw of a polymer in accordance with Example 15,

2.50 pbw of the diazo compound specified in Example 14 and

0.08 pbw of Crystal Violet base in

175.00 pbw of butanone

and heated at 100° C. in a drying oven, which process resulted in alayer thickness of 1.9 μm. The plate was exposed under a 5 kWmetal-halide lamp for 30 s at a distance of 110 cm through acontinuous-tone stepped wedge having 13 steps with a density gradationof 0.15, heated for 2 minutes at 100° C. and developed in the developerspecified in Example 13 for 60 s. A positive image of the film masterwas obtained; step 4 of the continuous-tone stepped wedge was completelyopen, while step 10 was reproduced in completely covered form. Astandard Ozasol® P 61 positive printing plate (Hoechst AG) used forcomparison had to be exposed for 70 s to achieve the same result.

EXAMPLE 17

The coated aluminum plate according to Example 16 was exposed under a 5kW metal-halide lamp for 30 s at a distance of 110 cm through acontinuous-tone stepped wedge having 13 steps with a density gradationof 0.15, heated for 2 minutes at 120° C. and developed by rubbing with asponge moistened with water. A perfect image of the film master wasobtained; step 2 of the continuous-tone stepped wedge was completelyopen, while step 6 was reproduced in completely covered form.

Although only a few exemplary embodiments of this invention have beendescribed in detail above, those skilled in the art will readilyappreciate that many modifications are possible in the exemplaryembodiments without materially departing from the novel teachings andadvantages of this invention. Accordingly, all such modifications areintended to be included within the scope of this invention.

What is claimed is:
 1. A compound of the formula I ##STR3## where R¹ isan alkyl radical, which is unsubstituted or substituted with at leastone member selected from the group consisting of a halogen atom, analkoxy group and a phenyl group,R² is a hydrogen atom or an optionallysubstituted alkyl radical containing 1 to 4 carbon atoms, R³ is alow-molecular weight, non-polymeric n-valent, aliphatic, cycloaliphatic,or aromatic radical, and n is an integer from 1 to
 4. 2. A compound ofthe formula I ##STR4## where R¹ is an optionally substituted alkylradical,R² is a hydrogen atom or an optionally substituted alkyl radicalcontaining 1 to 4 carbon atoms, n is an integer from 1 to 4, and R³ is aradical containing 1 to 3 aromatic nuclei.
 3. A compound as claimed inclaim 1, wherein R¹ is an alkyl radical containing 1 to 6 carbon atoms.4. A compound as claimed in claim 1, wherein R² is a hydrogen atom or amethyl group.
 5. A compound as claimed in claim 1, wherein R³ is analiphatic group.
 6. A compound as claimed in claim 5, wherein thealiphatic group of R³ has 1 to 10 carbon atoms.
 7. A compound as claimedin claim 1, wherein R³ is an aliphatic group interrupted by an etherealoxygen atom or phenylene group.
 8. A compound as claimed in claim 1,wherein R³ is an aliphatic group containing a double bond.
 9. A compoundas claimed in claim 1, wherein R³ is a cycloaliphatic group.
 10. Acompound as claimed in claim 9, wherein the cycloaliphatic groupcontains 5 or 6 ring members.
 11. A compound as claimed in claim 9,wherein the cycloaliphatic group contains one or two rings, which areoptionally linked.
 12. A compound as claimed in claim 1, wherein R² is ahydrogen atom.
 13. A compound as claimed in claim 1, wherein R² is anunsubstituted alkyl radical containing 1 to 4 carbon atoms.
 14. Acompound as claimed in claim 1, wherein R³ is an aromatic radical.
 15. Acompound as claimed in claim 14, wherein the aromatic radical contains 1to 3 aromatic nuclei which are joined to one another by fusing or by alinking intermediate member.
 16. A compound as claimed in claim 1,wherein R³ is selected from the group consisting of 4,4'-oxydiphenyl,1,3,5-benzenetriyl, 1,4-phenylene, 4-benzoylphenyl,4,4'-sulfonyldiphenyl, 4,4'-sulfonyloxydiphenyl, and biphenyl-4-4'-diyl.